US8715821B2 - Polymer article having a thin coating formed on at least one of its sides by plasma and method for producing such an article - Google Patents
Polymer article having a thin coating formed on at least one of its sides by plasma and method for producing such an article Download PDFInfo
- Publication number
- US8715821B2 US8715821B2 US11/917,620 US91762006A US8715821B2 US 8715821 B2 US8715821 B2 US 8715821B2 US 91762006 A US91762006 A US 91762006A US 8715821 B2 US8715821 B2 US 8715821B2
- Authority
- US
- United States
- Prior art keywords
- coating
- value
- sio
- plasma
- nanometers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active, expires
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
- C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
- B65D25/14—Linings or internal coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
- C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
- Y10T428/24975—No layer or component greater than 5 mils thick
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
Definitions
- the invention relates to a polymer article having a thin coating formed on at least one of its side by plasma and a method for manufacturing such an article.
- the invention relates also to a polymer article manufactured by the method, this article being of any shape and obtained by injection, extrusion molding, blow molding, compression molding, vacuum forming and the like.
- the invention relates more particularly to a method for manufacturing a polymer, preferentially either polypropylene or polyethylene, shaped article that is adapted to be used as a food container by having excellent surface properties such as reduced tendency of being stained, good resistance against chemicals, this container being washable in a dishwasher, and being also able to be placed either in a refrigerator, or in a freezer or a microwave oven.
- a plasma treatment is a chemical process wherein a gaseous compound in a given volume is decomposed under reduced atmosphere by an electrical glow discharge resulting in the coating of a thin film on the walls of a container.
- thin film means a film with a thickness less than a few hundreds of nanometers.
- PECVD Plasma Enhanced Chemical Vapor Deposition
- PECVD uses electrical energy to generate a glow discharge in which the energy is transferred into a gas mixture. This transforms the gas mixture into reactive radicals, ions, neutral atoms and molecules and other exited species.
- PECVD is largely used in electronics in depositing many films such as silicon nitride, diamond like carbon DLC, poly-silicon, amorphous silicon, silicon oxynitride, silicon oxide, silicon dioxide.
- plastics used for containers permits low molecular gas, such as oxygen and carbon dioxide, to permeate there through, and furthermore, plastic sorbs inside therein low molecular inorganic compound.
- aroma component can be absorbed inside the plastic; oxygen can gradually oxidize the content of the container, deterioring flavor, quality and purity of said content.
- silicon oxide films deposited by plasma enhanced chemical vapor deposition received considerable attention in the packaging industry due to their excellent gas barrier performance and their transparency.
- U.S. Pat. No. 3,442,686 discloses a flexible transparent packaging film which has extremely low permeability to gases and liquids, the film comprising, in combination, a flexible transparent organic polymeric base film, an adherent substantially gas and liquid impermeable intermediate coating of inorganic material on one surface of said base film and a sealable adherent top coating of organic polymeric material on said intermediate coating, said inorganic material being an oxide of silicon and said base film being polyester base film.
- oxide of silicon layer is transparent, it is also known to use oxide of silicon SiO x in order to improve the impermeability of polymeric films.
- U.S. Pat. No. 5,691,007 discloses a PECVD process whereby a coating of inorganic material may be placed on 3-D articles in a closely spaced matrix.
- This inorganic material can be a metal oxide such as SiO x wherein x is from about 1.4 to about 2.5; or an aluminum oxide based composition.
- the silicon oxide based composition is substantially dense and vapor-impervious and is desirably derived from volatile organosilicon compounds and an oxidizer such as oxygen or nitrous oxide.
- the thickness of the silicon oxide based material is about 50 to 400 nm.
- U.S. Pat. No. 6,338,870 discloses the use of HMDSO or tetra methyl disiloxane TMDSO for deposition of SiO x C y on PET laminated product wherein x is within the range of 1.5-2.2 and y is within the range of 0.15-0.80.
- an adhesion promoter layer which is a first plasma polymerized organosilicon compound deposited on the surface of the substrate in the substantial absence of oxygen, the organosilicon compound being preferentially tetramethyldisiloxane,
- a protection coating layer which is a second plasma polymerized organosilicon compound deposited on the surface of the adhesion promoter layer in the presence of a sufficient stoichiometric excess of oxygen to form a silicon polymer of SiO 1.8-2.4 C 0.3-1.0 H 0.7-4.0 .
- the organosilicon compound is preferentially tetramethyldisiloxane
- SiO x layer which is a layer of a plasma polymerized tetramethyldisiloxane deposited on the surface of the protective coating layer.
- a first condensed plasma zone of SiO x C y H z wherein x is from 1 to 2.4, y is from 0.2 to 2.4 and z is from zero to 4 on the polymeric substrate wherein the plasma is generated from an organosilane compound in an oxidizing atmosphere and
- the plasma formed barrier is then a continuum of a plasma deposited coating having a composition which varies from SiO x C y H z at the interface between the plasma layer and the polymeric surface to SiO x , which is the new surface of the container.
- This substrate is used for polymer bottle, particularly the non refillable bottle used for carbonated beverages, the aim of the coating being to be a barrier to the permeation of odorants, flavorants, ingredients, gas and water vapor. It is contended that the condensed plasma coatings of this prior art document may be applied on any suitable substrate including polyolefin such as polypropylene or polyethylene.
- examples 1 to 7 in this prior art document are plasma coatings on PET, no information being given for examples 8 a , 8 b and 8 c as regards the polymer used, a 150 microns HDPE film being mentioned in example 9, PET films being used in example 10, polycarbonate being used for the last examples 11 to 13.
- the reacting gas used like HMDSO are liquids with a low vapor pressure at ambient temperature.
- the use of theses gases requires a carrying gas like argon to transport the vapor from the container towards the reacting chamber.
- it is necessary to heat the gas line to avoid the condensation of the gas between the container and the reacting chamber.
- the present inventor have noticed that it remains particularly difficult to obtain SiO x or SiO x C y H z layers with good adhesion properties on some polymer substrate, especially polypropylene, using the PECVD route.
- the adhesion promoter layer has a thickness of about 100 nm to about 200 nm and the protective coating layer has a thickness of not less than about 0.1 micron and not greater than about 2 microns.
- An object of the present invention is to provide a coating for a polymer article and a method for manufacturing a polymer article having a coating according to the present invention.
- Another object of the invention is to provide a polymer article with a coating according to the present invention which is not washed out in a dishwasher, i.e. which is wash-resistant.
- An object of the invention is to provide a coating with a good steam-resistance
- Another object of the invention is to provide a coating with a good adhesion on a polymer substrate with no detachment.
- Another object of the invention is to provide a polymer article which remains transparent after several washes in a dishwasher.
- Another object of the present invention is to provide a polymer article incorporating a coating with a reduced wall thickness while maintaining a suitable barrier to the permeation of odorants, flavorants, ingredients, gas and water vapor.
- Another object of the present invention is a method for manufacturing a polymer article having a thin coating formed on at least one of its side by plasma, this article being able to be placed either in a refrigerator or in a freezer or in a microwave oven.
- An object of the invention is to provide a reacting gas which is stable and does not react in contact with oxygen.
- An object of the invention is to provide a reacting gas which is at a sufficient saturation vapor pressure in order to be moved from a storage place to a reacting chamber without adding a carrier gas.
- An object of the invention is to provide a reacting gas which does not need to be heated during its moving from a storage place to a reacting chamber in order to avoid the condensation of said reacting gas.
- An object of the invention is to provide a reacting gas with no spontaneous combustion.
- An object of the invention is to provide a coating with a better control of the oxygen percentage in the coating.
- the method according to the invention for manufacturing a polymer article having a thin coating formed on at least one of its side by plasma characterized in that said method comprises successively:
- the oxygen percentage in the coating is easily controlled as the tetramethylsilane does not contain any oxygen element. So the oxygen percentage in the coating layer is only controlled by the flow of the oxidizing gas.
- the tetramethylsilane is usable as such, i.e. without adding a carrier gas between a storage place to the reacting chamber.
- the polymer article is made in polypropylene or polyethylene.
- the coating is made using either magnetic guidance, or a plasma generating electrode, or both magnetic guidance and a plasma generating electrode.
- power is loaded to the plasma using a frequency of 13.56 MHz.
- the ratio between oxygen and tetramethylsilane is maintained during a first step of around one to four seconds at its first value of around zero to four, said ratio being maintained during a second step of around five to thirty seconds at its second value of around four to ten.
- FIG. 1 shows apparatus for producing layers on an article.
- a 3D polypropylene container of the type used for food is placed in a vacuum chamber thus defining an internal volume, the internal volume forming the reaction chamber for the plasma treatment.
- plasma treatment means the chemical decomposition of a gaseous compound by an electrical glow discharge under reduced atmosphere. Through a plasma treatment, it is obtained a layer or coating over the internal walls of the container in which the pressure has been reduced and the electrical glow discharge has taken place.
- the apparatus 1 for producing the coating according the invention comprises a support plate 2 overcoated by a radiofrequency faraday shield 3 having a radiofrequency electrode 5 supported by isolation means 6 provided on the support plate 2 .
- the electrode 5 is connected to a radiofrequencies generator 4 , known as such.
- the electrode 5 has an internal shaped wall 7 on which the article to be coated 8 is placed.
- the internal shaped wall 7 has a complementary form of the form of article 8 .
- the article to be coated 8 forms an internal volume 9 which is the reacting chamber in which gas from an inlet 10 is injected.
- Pressure is gradually reduced inside the reaction chamber 9 to a value of around 0.01 mbar. Reaction gases are then introduced through the gas inlet 10 in the reaction chamber 9 until a pressure of about 0.1 mbar.
- argon plasma treatment is made on the inner surface of the 3D container.
- the argon plasma treatment is between 1 and 20 s, more preferentially between 5 and 10 s.
- the argon plasma treatment increases the energy on the surface in order to obtain a better adherence on it of a plasma deposition.
- a first plasma deposit is made on the plasma treated inner surface of the container, using, tetramethylsilane Si—(CH 3 ) 4 and oxygen O 2 both injected at a given flow rate in said internal volume of the container forming the reaction chamber.
- power is loaded to the plasma by radiofrequency, the frequency being of 13.56 MHz.
- the ratio between oxygen and tetramethylsilane is between zero and three in the vacuum chamber and the treatment time is between one to four seconds.
- the tetramethylsilane has a saturation vapor pressure of around 900 mbar at ambient temperature and does not need to be added in a carrier gas in order to be moved from a storage place to the reacting chamber 9 .
- the chemical composition of this first SiO x C y H z coating is the following:
- Electron Spectroscopy for Chemical Analysis (ESCA), Infrared Transmission (FTIR) and Electron Recoil Detection (ERD) analyses have been used.
- a second plasma deposit is then made on the coated inner surface of the container, using tetramethylsilane and oxygen again. Power is again loaded by RF, same frequency being used.
- the ratio between oxygen and tetramethylsilane in said internal volume of the container forming the reaction chamber is maintained between four and ten, i.e. the oxygen flow rate in said internal volume is between four and ten times bigger than the tetramethylsilane flow rate in said internal volume and the treatment time is between five to thirty seconds.
- the ratio between oxygen and tetramethylsilane is between four and seven.
- the ratio between oxygen and tetramethylsilane is between around zero and three so as to obtain said first coating and the ratio is between around four and ten so as to obtain said second coating onto said first one.
- the second deposit is a SiO x C y H z layer (or coating) of a few nanometers thick. More precisely, the thickness of said second SiO x C y H z coating is from about 10 nanometers to about 100 nanometers, preferentially from 15 to 50 nanometers, and more preferentially around 30 nanometers.
- the chemical composition of this second SiO x C y H z coating is the following (ESCA, FTIR and ERD analyses):
- the reduced atmosphere is increased to the ambient atmosphere.
- the present inventor has surprisingly discovered that the shaped article obtained has a very low tendency of being stained during its lifetime, this shaped article being washable in a dishwasher, and being also able to be placed in a refrigerator, a freezer or a microwave oven.
- Neodisher Alka 300 A number of 125 washings were made at 85° C. using a detergent named Neodisher Alka 300 and a rinsing liquid agent named Neodisher TS, supplied by Dr Weigert Cie.
- bowls have been filled with-different kind of aggressive alimentary sauces and coloring products and then stocked in an oven at 80° C. during 24 hours.
- the method for manufacturing a polymer article having a thin coating formed on at least one of its side by plasma according to the present invention comprises successively:
- the method according the invention comprises before said step of plasma treatment on said polymer article, the following steps of:
- a first coating of SiO x C y H z which is either a plasma polymerized tetramethylsilane or a plasma polymerized tetramethylsilane and an oxidizing gas, preferentially oxygen or carbon dioxide, deposited on the surface on a polymer article, with an x value between 0 and 1.7, an y value between 0.5 and 0.8, and an z value between 0.35 and 0.6 for said first SiO x C y H z coating is highly preferential and that a second coating of SiO x C y H z which is a plasma polymerized tetramethylsilane and an oxidizing gas, preferentially oxygen or carbon dioxide, deposited on the surface on the first coating, with an x value between 1.7 and 1.99, an y value between 0.2 and 0.7, and an z value between 0.2 and 0.35 for said second SiO x C y H z coating is highly preferential.
- the polymer article may be in either polypropylene or polyethylene or polycarbonate or poly butyl teraphtalate.
- the coating according to the invention may be made using either magnetic guidance, or a plasma generating electrode, or both magnetic guidance and a plasma generating electrode.
- the polymer article is a 3D shaped one, this article being placed in a vacuum chamber and defining an internal volume and an external volume, the inner part of the article defining the internal volume as the reacting chamber, pressure inside said reacting chamber being around 0.01 mbar.
- a method with an argon plasma treatment made on the inner surface of a 3D polyethylene container and a plasma deposition of one coating made on the inner surface using tetramethysilane and oxygen also results in the formation of a container having very low tendency of being stained during its lifetime and being washable in a dishwasher and able to be placed in a refrigerator, a freezer or a microwave oven.
- the ratio between oxygen and tetramethylsilane in the internal volume of the container forming the reaction chamber is maintained between four and ten, i.e. the oxygen flow rate in said internal volume is between four and ten times bigger than the tetramethylsilane flow rate in said internal volume and the treatment time is between five to thirty seconds.
- the ratio between oxygen and tetramethylsilane is between four and seven.
- the layer is a SiO x C y H z layer (or coating) of a few nanometers thick. More precisely, the thickness of said Sio x C y H z coating is from about 10 nanometers to about 100 nanometers, preferentially from 15 to 50 nanometers, and more preferentially around 30 nanometers.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Toxicology (AREA)
- Chemical Vapour Deposition (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Physical Vapour Deposition (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
Description
-
- a plasma treatment on said polymer article, advantageously an argon plasma treatment;
- a deposition of a first coating of SiOxCyHz by generation of a plasma either from tetramethylsilane, or from tetramethylsilane and an oxidizing gas, preferentially oxygen or carbon dioxide, the x value being between 0 and 1.7, the y value being between 0.5 and 0.8, the z value being between 0.35 and 0.6 for said first SiOxCyHz coating, and
- a subsequent deposition of a second coating of SiOxCyHz by generation of a plasma from tetramethylsilane in the presence of an oxidizing gas, preferentially oxygen O2 or carbon dioxide CO2, the x value being between 1.7 and 1.99, the y value being between 0.2 and 0.7, the z value being between 0.2 and 0.35 for said second SiOxCyHz coating, the thickness of said first coating being from about 1 nanometer to about 15 nanometers and the thickness of said second coating being from about 10 nanometers to about 100 nanometers, preferentially around 30 nanometers.
-
- a plasma treatment on said polymer article, advantageously an argon plasma treatment ;
- a deposition of a first coating of SiOxCyHz by generation of a plasma from tetramethylsilane, preferentially in the presence of an oxidizing gas, preferentially oxygen O2 or carbon dioxyde, the x value being between 0 and 1.7, the y value being between 0.5 and 0.8, the z value being between 0.35 and 0.6 for said first SiOxCyHz coating, and
- a subsequent deposition of a second coating of SiOxCyHz by generation of a plasma from tetramethylsilane in the presence of an oxidizing gas, preferentially oxygen O2 or carbon dioxide, the x value being between 1.7 and 1.99, the y value being between 0.2 and 0.7, the z value being between 0.2 and 0.35 for said second SiOxCyHz coating, the thickness of said first coating being from about 1 nanometer to about 15 nanometers and the thickness of said second coating being from about 10 nanometers to about 100 nanometers, preferentially around 30 nanometers.
-
- placing a polymer article in a vacuum chamber;
- decreasing the pressure in the vacuum chamber;
- decreasing the pressure in the internal volume of the polymer article;
- applying an electrical glow discharge through an electrode disposed around the container closely to its external surface.
Claims (13)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EPPCT/EP2005/007063 | 2005-06-16 | ||
PCT/EP2005/007063 WO2006133730A1 (en) | 2005-06-16 | 2005-06-16 | Method for producing coated polymer |
WOPCT/EP2005/007063 | 2005-06-16 | ||
PCT/IB2006/002483 WO2007072120A1 (en) | 2005-06-16 | 2006-06-16 | Polymer article having a thin coating formed on at least one of its side by plasma and method for producing such article |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2006/002483 A-371-Of-International WO2007072120A1 (en) | 2005-06-16 | 2006-06-16 | Polymer article having a thin coating formed on at least one of its side by plasma and method for producing such article |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/195,949 Division US9302816B2 (en) | 2005-06-16 | 2014-03-04 | Polymer article having a thin coating formed on at least one of its sides by plasma and method for producing such an article |
Publications (2)
Publication Number | Publication Date |
---|---|
US20090042025A1 US20090042025A1 (en) | 2009-02-12 |
US8715821B2 true US8715821B2 (en) | 2014-05-06 |
Family
ID=37531966
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/917,620 Active 2029-04-27 US8715821B2 (en) | 2005-06-16 | 2006-06-16 | Polymer article having a thin coating formed on at least one of its sides by plasma and method for producing such an article |
US14/195,949 Active 2026-08-01 US9302816B2 (en) | 2005-06-16 | 2014-03-04 | Polymer article having a thin coating formed on at least one of its sides by plasma and method for producing such an article |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/195,949 Active 2026-08-01 US9302816B2 (en) | 2005-06-16 | 2014-03-04 | Polymer article having a thin coating formed on at least one of its sides by plasma and method for producing such an article |
Country Status (16)
Country | Link |
---|---|
US (2) | US8715821B2 (en) |
EP (2) | EP1893788B1 (en) |
JP (1) | JP5023056B2 (en) |
KR (1) | KR101326496B1 (en) |
CN (1) | CN101198722B (en) |
AU (1) | AU2006327910B2 (en) |
BR (1) | BRPI0611779B1 (en) |
CA (1) | CA2612167C (en) |
DK (1) | DK2597175T3 (en) |
ES (1) | ES2601954T3 (en) |
HU (1) | HUE029458T2 (en) |
PH (1) | PH12007502678B1 (en) |
PL (2) | PL2597175T3 (en) |
PT (1) | PT2597175T (en) |
RU (1) | RU2417274C2 (en) |
WO (2) | WO2006133730A1 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006133730A1 (en) * | 2005-06-16 | 2006-12-21 | Innovative Systems & Technologies | Method for producing coated polymer |
US7878054B2 (en) * | 2007-02-28 | 2011-02-01 | The Boeing Company | Barrier coatings for polymeric substrates |
US8197909B2 (en) * | 2008-08-26 | 2012-06-12 | Ford Global Technologies, Llc | Plasma coatings and method of making the same |
DE102011017404A1 (en) * | 2011-04-18 | 2012-10-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for depositing a transparent barrier layer system |
CN102241827B (en) * | 2011-05-14 | 2013-03-20 | 中南林业科技大学 | Adjusting method of natural vegetable fiber and polylactic acid interface |
CN103732337B (en) * | 2011-08-26 | 2017-03-08 | 埃克阿泰克有限责任公司 | Organic resin laminate, manufacture and the method using this Organic resin laminate |
US20150183254A1 (en) * | 2012-05-29 | 2015-07-02 | Lg Chem, Ltd. | Silicone blanket for printing and method of manufacturing the same |
CN104752633A (en) * | 2013-12-31 | 2015-07-01 | 中国科学院微电子研究所 | Thin film packaging method |
JP6467867B2 (en) * | 2014-10-30 | 2019-02-13 | 凸版印刷株式会社 | Transparent gas barrier film |
JP6532450B2 (en) * | 2016-12-06 | 2019-06-19 | 株式会社アルバック | Deposition method |
US11432869B2 (en) * | 2017-09-22 | 2022-09-06 | Covidien Lp | Method for coating electrosurgical tissue sealing device with non-stick coating |
IL312016A (en) * | 2021-10-25 | 2024-06-01 | Adama Makhteshim Ltd | Method and composition for reducing solvent release from, and reducing odor of, agrochemical formulations |
EP4289519A1 (en) | 2022-06-10 | 2023-12-13 | Basf Se | Plasma-created barriers for packaging |
Citations (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3442686A (en) | 1964-03-13 | 1969-05-06 | Du Pont | Low permeability transparent packaging films |
US3485666A (en) | 1964-05-08 | 1969-12-23 | Int Standard Electric Corp | Method of forming a silicon nitride coating |
US4830873A (en) | 1984-04-06 | 1989-05-16 | Robert Bosch Gmbh | Process for applying a thin, transparent layer onto the surface of optical elements |
US5000113A (en) | 1986-12-19 | 1991-03-19 | Applied Materials, Inc. | Thermal CVD/PECVD reactor and use for thermal chemical vapor deposition of silicon dioxide and in-situ multi-step planarized process |
JPH03107458A (en) | 1989-09-22 | 1991-05-07 | Suzuki Motor Corp | Method for forming film on inside surface of plastic container |
FR2670506A1 (en) | 1990-12-17 | 1992-06-19 | Air Liquide | Process for depositing a layer of silicon oxide bonded to a polyolefin substrate |
JPH05279504A (en) | 1991-02-28 | 1993-10-26 | Suzuki Motor Corp | Production of resin bumper |
US5378510A (en) | 1992-05-28 | 1995-01-03 | Polar Materials Inc. | Methods and apparatus for depositing barrier coatings |
JPH0732531A (en) | 1993-07-23 | 1995-02-03 | Kuwabara Yasunaga | Gas blocking plastic material provided with transparent membrane composed of silicon compound and production thereof |
EP0787828A2 (en) | 1996-01-30 | 1997-08-06 | Becton, Dickinson and Company | Apparatus and method for plasma processing |
US5691007A (en) | 1996-09-30 | 1997-11-25 | Becton Dickinson And Company | Process for depositing barrier film on three-dimensional articles |
US5718967A (en) | 1995-10-13 | 1998-02-17 | The Dow Chemical Company | Coated plastic substrate |
US5900284A (en) | 1996-07-30 | 1999-05-04 | The Dow Chemical Company | Plasma generating device and method |
WO2001094448A2 (en) | 2000-06-06 | 2001-12-13 | The Dow Chemical Company | Barrier layer for polymers and containers |
US6338870B1 (en) | 1999-04-07 | 2002-01-15 | Tetra Laval Holdings & Finance S.A. | Packaging laminate with gas and aroma barrier properties |
FR2814382A1 (en) | 2000-09-28 | 2002-03-29 | Cebal | METHOD FOR DEPOSITING AN INTERNAL COATING IN A PLASTIC CONTAINER |
US20030044552A1 (en) | 2001-06-08 | 2003-03-06 | Minoru Komada | Gas barrier film |
US20030157345A1 (en) | 2000-08-01 | 2003-08-21 | Nasser Beldi | Plasma deposited barrier coating comprising an interface layer, method of obtaining same and container coated therewith |
US20030165696A1 (en) | 2001-05-11 | 2003-09-04 | Tsunehisa Namiki | Silicon oxide membrane |
US20030215652A1 (en) | 2001-06-04 | 2003-11-20 | O'connor Paul J. | Transmission barrier layer for polymers and containers |
WO2004044039A2 (en) * | 2002-11-12 | 2004-05-27 | Dow Global Technologies Inc. | Process and apparatus for depositing plasma coating onto a container |
DE10258678A1 (en) | 2002-12-13 | 2004-07-08 | Schott Glas | Process for applying alternating layers e.g. barrier layers onto a plastic bottle by chemical gas phase deposition comprises depositing an organic adhesion promoting layer on a substrate and applying an inorganic barrier layer |
US20040253451A1 (en) * | 2003-02-10 | 2004-12-16 | Sayaka Kawashima | Barrier film |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02214017A (en) * | 1989-02-10 | 1990-08-27 | Hitachi Maxell Ltd | Magnetic recording tape |
CA2048168A1 (en) | 1990-08-03 | 1992-02-04 | John T. Felts | Silicon oxide based thin film vapour barriers |
WO2006133730A1 (en) * | 2005-06-16 | 2006-12-21 | Innovative Systems & Technologies | Method for producing coated polymer |
-
2005
- 2005-06-16 WO PCT/EP2005/007063 patent/WO2006133730A1/en active Application Filing
-
2006
- 2006-06-16 PT PT131557522T patent/PT2597175T/en unknown
- 2006-06-16 BR BRPI0611779-1A patent/BRPI0611779B1/en active IP Right Grant
- 2006-06-16 CN CN2006800215007A patent/CN101198722B/en active Active
- 2006-06-16 WO PCT/IB2006/002483 patent/WO2007072120A1/en active Application Filing
- 2006-06-16 KR KR1020077030647A patent/KR101326496B1/en active IP Right Grant
- 2006-06-16 ES ES13155752.2T patent/ES2601954T3/en active Active
- 2006-06-16 EP EP06795456.0A patent/EP1893788B1/en active Active
- 2006-06-16 US US11/917,620 patent/US8715821B2/en active Active
- 2006-06-16 JP JP2008516450A patent/JP5023056B2/en not_active Expired - Fee Related
- 2006-06-16 RU RU2008101700/02A patent/RU2417274C2/en not_active IP Right Cessation
- 2006-06-16 EP EP13155752.2A patent/EP2597175B1/en active Active
- 2006-06-16 HU HUE13155752A patent/HUE029458T2/en unknown
- 2006-06-16 PL PL13155752T patent/PL2597175T3/en unknown
- 2006-06-16 DK DK13155752.2T patent/DK2597175T3/en active
- 2006-06-16 PL PL06795456T patent/PL1893788T3/en unknown
- 2006-06-16 PH PH12007502678A patent/PH12007502678B1/en unknown
- 2006-06-16 CA CA2612167A patent/CA2612167C/en not_active Expired - Fee Related
- 2006-06-16 AU AU2006327910A patent/AU2006327910B2/en not_active Ceased
-
2014
- 2014-03-04 US US14/195,949 patent/US9302816B2/en active Active
Patent Citations (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3442686A (en) | 1964-03-13 | 1969-05-06 | Du Pont | Low permeability transparent packaging films |
US3485666A (en) | 1964-05-08 | 1969-12-23 | Int Standard Electric Corp | Method of forming a silicon nitride coating |
US4830873A (en) | 1984-04-06 | 1989-05-16 | Robert Bosch Gmbh | Process for applying a thin, transparent layer onto the surface of optical elements |
US5000113A (en) | 1986-12-19 | 1991-03-19 | Applied Materials, Inc. | Thermal CVD/PECVD reactor and use for thermal chemical vapor deposition of silicon dioxide and in-situ multi-step planarized process |
JPH03107458A (en) | 1989-09-22 | 1991-05-07 | Suzuki Motor Corp | Method for forming film on inside surface of plastic container |
FR2670506A1 (en) | 1990-12-17 | 1992-06-19 | Air Liquide | Process for depositing a layer of silicon oxide bonded to a polyolefin substrate |
JPH05279504A (en) | 1991-02-28 | 1993-10-26 | Suzuki Motor Corp | Production of resin bumper |
US5378510A (en) | 1992-05-28 | 1995-01-03 | Polar Materials Inc. | Methods and apparatus for depositing barrier coatings |
JPH0732531A (en) | 1993-07-23 | 1995-02-03 | Kuwabara Yasunaga | Gas blocking plastic material provided with transparent membrane composed of silicon compound and production thereof |
US5718967A (en) | 1995-10-13 | 1998-02-17 | The Dow Chemical Company | Coated plastic substrate |
EP0787828A2 (en) | 1996-01-30 | 1997-08-06 | Becton, Dickinson and Company | Apparatus and method for plasma processing |
US5900284A (en) | 1996-07-30 | 1999-05-04 | The Dow Chemical Company | Plasma generating device and method |
US5691007A (en) | 1996-09-30 | 1997-11-25 | Becton Dickinson And Company | Process for depositing barrier film on three-dimensional articles |
US6338870B1 (en) | 1999-04-07 | 2002-01-15 | Tetra Laval Holdings & Finance S.A. | Packaging laminate with gas and aroma barrier properties |
US20020028336A1 (en) | 1999-04-07 | 2002-03-07 | Bertrand Jaccoud | Packaging laminate with gas and aroma barrier properties |
US20040086725A1 (en) * | 1999-04-07 | 2004-05-06 | Bertrand Jaccoud | Packaging laminate with gas and aroma barrier properties |
WO2001094448A2 (en) | 2000-06-06 | 2001-12-13 | The Dow Chemical Company | Barrier layer for polymers and containers |
US20020006487A1 (en) * | 2000-06-06 | 2002-01-17 | O'connor Paul J. | Transmission barrier layer for polymers and containers |
US20030157345A1 (en) | 2000-08-01 | 2003-08-21 | Nasser Beldi | Plasma deposited barrier coating comprising an interface layer, method of obtaining same and container coated therewith |
FR2814382A1 (en) | 2000-09-28 | 2002-03-29 | Cebal | METHOD FOR DEPOSITING AN INTERNAL COATING IN A PLASTIC CONTAINER |
US20030165696A1 (en) | 2001-05-11 | 2003-09-04 | Tsunehisa Namiki | Silicon oxide membrane |
US20030215652A1 (en) | 2001-06-04 | 2003-11-20 | O'connor Paul J. | Transmission barrier layer for polymers and containers |
US20030044552A1 (en) | 2001-06-08 | 2003-03-06 | Minoru Komada | Gas barrier film |
WO2004044039A2 (en) * | 2002-11-12 | 2004-05-27 | Dow Global Technologies Inc. | Process and apparatus for depositing plasma coating onto a container |
DE10258678A1 (en) | 2002-12-13 | 2004-07-08 | Schott Glas | Process for applying alternating layers e.g. barrier layers onto a plastic bottle by chemical gas phase deposition comprises depositing an organic adhesion promoting layer on a substrate and applying an inorganic barrier layer |
US20040253451A1 (en) * | 2003-02-10 | 2004-12-16 | Sayaka Kawashima | Barrier film |
Non-Patent Citations (3)
Title |
---|
Barreca, Davide, et al., "Low-Temperature PECVD of Transparent SiOxCyHz Thin Films", Chem Vap Deposition, 2007, 13, pp. 205-210. |
Inque et al, "In Situ Observation of Behavior of Organosilicon Molecules in Low-temperature Plasma Enhanced CVD", vol. 345, No. 1, pp. 90-93, May 1999. |
Teshima et al, "Growth and Structure of Silica Films Deposited on a Polymeric Material by Plasma-enhanced Chemical Vapor Deposition", vol. 420-421, pp. 324-329, Dec. 2002. |
Also Published As
Publication number | Publication date |
---|---|
US20140255676A1 (en) | 2014-09-11 |
EP1893788B1 (en) | 2014-12-24 |
US20090042025A1 (en) | 2009-02-12 |
ES2601954T3 (en) | 2017-02-16 |
CN101198722A (en) | 2008-06-11 |
PT2597175T (en) | 2016-11-16 |
PL2597175T3 (en) | 2017-02-28 |
JP5023056B2 (en) | 2012-09-12 |
CA2612167A1 (en) | 2007-06-28 |
RU2008101700A (en) | 2009-07-27 |
WO2007072120A1 (en) | 2007-06-28 |
US9302816B2 (en) | 2016-04-05 |
AU2006327910A1 (en) | 2007-06-28 |
KR101326496B1 (en) | 2013-11-08 |
CN101198722B (en) | 2010-12-08 |
EP1893788A1 (en) | 2008-03-05 |
RU2417274C2 (en) | 2011-04-27 |
DK2597175T3 (en) | 2016-12-05 |
HUE029458T2 (en) | 2017-02-28 |
PL1893788T3 (en) | 2015-05-29 |
AU2006327910B2 (en) | 2011-12-01 |
EP2597175A1 (en) | 2013-05-29 |
CA2612167C (en) | 2015-01-13 |
EP2597175B1 (en) | 2016-08-10 |
KR20080025090A (en) | 2008-03-19 |
JP2008544011A (en) | 2008-12-04 |
BRPI0611779B1 (en) | 2017-10-10 |
WO2006133730A1 (en) | 2006-12-21 |
BRPI0611779A2 (en) | 2010-09-28 |
PH12007502678B1 (en) | 2013-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9302816B2 (en) | Polymer article having a thin coating formed on at least one of its sides by plasma and method for producing such an article | |
US20020006487A1 (en) | Transmission barrier layer for polymers and containers | |
JP5362941B2 (en) | Composite materials with improved chemical resistance | |
KR101162377B1 (en) | Chemical vapor deposition film formed by plasma cvd process and method for forming same | |
US20030215652A1 (en) | Transmission barrier layer for polymers and containers | |
CN100381606C (en) | Rapid process for producing multilayer barrier coatings | |
US7906217B2 (en) | Vapor deposited film by plasma CVD method | |
JP2004504938A (en) | Plasma-deposited barrier coating with a boundary layer, method for obtaining such a coating, and a container thus obtained | |
JP4887808B2 (en) | Deposition film by plasma CVD method | |
KR100545908B1 (en) | Barrier coating | |
JP4403093B2 (en) | Composite material and method of manufacturing the same | |
DK1893788T3 (en) | POLYMER ARTICLE WITH A THIN COATING MADE ON AT LEAST ITS PLASMA SIDE | |
US20080145651A1 (en) | Method for Manufacturing a Pecvd Carbon Coated Polymer Article and Article Obtained by Such Method | |
JP3864126B2 (en) | Inner coated polyester resin container |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: INNOVATIVE SYSTEMS & TECHNOLOGIES, FRANCE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BELDI, NASSER;CHOLLET, PATRICK;REEL/FRAME:020347/0084 Effective date: 20071215 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551) Year of fee payment: 4 |
|
AS | Assignment |
Owner name: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT, ILLINOIS Free format text: SECURITY INTEREST;ASSIGNOR:DART INDUSTRIES INC.;REEL/FRAME:052460/0739 Effective date: 20200417 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 8 |
|
AS | Assignment |
Owner name: WELLS FARGO BANK, NATIONAL ASSOCIATION, AS ADMINISTRATIVE AGENT, COLORADO Free format text: SECURITY INTEREST;ASSIGNORS:TUPPERWARE BRANDS CORPORATION;DART INDUSTRIES INC.;REEL/FRAME:058963/0285 Effective date: 20211123 Owner name: DART INDUSTRIES INC., FLORIDA Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT;REEL/FRAME:058517/0379 Effective date: 20211123 Owner name: TUPPERWARE BRANDS CORPORATION, FLORIDA Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT;REEL/FRAME:058517/0379 Effective date: 20211123 |